WO2017072358A1 - Lingette hautement active de détergent universel à trois phases et procédé pour sa fabrication - Google Patents

Lingette hautement active de détergent universel à trois phases et procédé pour sa fabrication Download PDF

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Publication number
WO2017072358A1
WO2017072358A1 PCT/EP2016/076224 EP2016076224W WO2017072358A1 WO 2017072358 A1 WO2017072358 A1 WO 2017072358A1 EP 2016076224 W EP2016076224 W EP 2016076224W WO 2017072358 A1 WO2017072358 A1 WO 2017072358A1
Authority
WO
WIPO (PCT)
Prior art keywords
dispersion
phase
carrier material
solid
detergent
Prior art date
Application number
PCT/EP2016/076224
Other languages
German (de)
English (en)
Inventor
Michael Pulina
Original Assignee
Coin Consulting Ug (Haftungsbeschränkt)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coin Consulting Ug (Haftungsbeschränkt) filed Critical Coin Consulting Ug (Haftungsbeschränkt)
Priority to ES16788534T priority Critical patent/ES2952137T3/es
Priority to EP16788534.2A priority patent/EP3368648B1/fr
Priority to PL16788534.2T priority patent/PL3368648T3/pl
Priority to RU2018112140A priority patent/RU2018112140A/ru
Priority to US15/771,042 priority patent/US20180320114A1/en
Priority to JP2018541522A priority patent/JP2018534413A/ja
Priority to CN201680063870.0A priority patent/CN108473923A/zh
Publication of WO2017072358A1 publication Critical patent/WO2017072358A1/fr
Priority to IL258887A priority patent/IL258887B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049Cleaning or scouring pads; Wipes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06BTREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/10Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by contact with a member carrying the treating material
    • D06B1/12Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by contact with a member carrying the treating material by rubbing contact, e.g. with brushes or pads
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof

Definitions

  • the present invention relates to a laundry cloth and a process for its preparation and in particular a highly active three-phase heavy duty detergent cloth with
  • Raw material mixtures in focus The optimization of the cleaning performance is characterized in particular by the possibility of extending a hygienically clean state and improving a degree of cleaning.
  • liquid detergents in their cleaning properties could not reach the level of cleaning of a heavy-duty detergent (ie a solid mixture) until today. This is based on the limitation of a liquid detergent to liquid or water-soluble components. The crucial missing substance in one
  • Liquid detergent is the group of zeolites and their substitutes (e.g., phyllosilicates and their derivatives). These assist in soil adsorption and water hardness reduction in use.
  • a current product trend is the way in which the detergent is portioned. This can be done firstly by the packaging of a liquid detergent in small polymer bags. However, the above problem of the missing zeolite remains. Another physical modification of the detergent is to mix a detergent with a fatty alcohol so that desired shapes can be achieved. However, both product concepts describe a single-phase product that can only be differentiated by portioning.
  • Applicant's DE 10 2013 014 015 discloses a significant further development in the form of a three-phase heavy duty washcloth consisting of a dispersion (ie a solid phase liquid continuous phase) and a solid substrate. The dispersion is applied to a solid at room temperature carrier material.
  • Support material may be both a nonwoven and a fatty alcohol or a substrate for the phase combination of a dispersion with another separate phase.
  • the first phase of the dispersion is thus a liquid detergent concentrate consisting of washing-active
  • the second phase of the dispersion is a
  • Soil adsorption e.g., zeolite
  • the third phase is one at
  • the solid phase of the dispersion i. the second phase, represents a functional part of the full-strength wash cloth.
  • the substrate is used for statistical fixation of the dispersion and consists of a
  • the object of the present invention was thus to provide a three-phase heavy-duty detergent and a method for its production with increased
  • Room temperature solid support material (4) is applied, characterized by the following steps: (a) providing a liquid detergent lotion (1) with exothermic saponified ingredients and a water content of 10 to 30 wt .-%; (b) adding solid additives (2) to the liquid detergent lotion (1) by means of a dispersing agent so that the dispersion (3) is formed with a solids content of 1-10% by weight; (c) applying the dispersion (3) to the carrier material (4) by means of a moistening device (5) so that the carrier material (4) statistically fixes the dispersion (3); wherein the steps (a) - (c) are carried out at room temperature and wherein the ratio of the average particle size of the solid additives (2) to the diameter and the gap width (6) of the openings of the
  • Humidifying device (5) is between 5 * 10 "4 : 1 and 15 * 10 " 4 : 1.
  • the object has also been achieved by a three-phase heavy duty cloth according to claim 10 and by a system of a cloth and a moistening device for its manufacture according to claim 18.
  • detergent lotion means a composition which comprises one or more biocatalysts, preferably enzymes or cell extracts, in particular enzymes which are suitable for the production of detergents or cleaners
  • room temperature means according to the invention a temperature range at which biocatalysts are not irreversibly inactivated, preferably about 5-50 ° C., more preferably about 15-30 ° C.
  • suspension preferably means a suspension, more preferably a suspension with a liquid phase as a continuous phase.
  • exothermic saponified constituents means exothermically saponified or neutralized moieties, preferably exothermically saponified or neutralized
  • average particle size means according to the invention the mean
  • Particle size D50 based on the arithmetic mean and can be e.g. determined by means of a laser diffractometer "Mastersizer TM 2000S” Malvern Instruments Ltd., (Malvern, Worcestershire, United Kingdom), according to the manufacturer according to ISO 13320: 2009 (see, for example, document ID 7.1.1.2.acl33.E the Fa. PQ Corporation (Valleybrooke Corporate Center, Malvern, PA 19355-1740, USA)).
  • Sustainability features through the conservation of resources, the distribution (CC balance), the application by the consumer (dosage), as well as the energy balance in production. Transformed into technical features, this means that it is expedient to realize a lightweight, compact detergent that can be produced in a cold process. The object of the present invention is therefore to be deduced from the sustainability features described below.
  • the previous dosage forms of the detergent can be divided into the groups of powders, liquid detergents and Fertigdosierwaschsch (such as.
  • Composition are powders and the like. Characterized in that a portion of the formulation of sodium sulfate o.ä. Substances that are used to increase the flowability of the powder - a function in terms of washing activity, these materials do not have. Liquid detergents in turn use a not inconsiderable amount of water, which can be justified by the viscosity, flowability and thus easy dosage to be achieved.
  • the Fertigdosierwaschsch in the form of liquid detergent filled polymer bags usually have a high proportion of water or solubilizers (eg propylene glycol, glycerol) and just the polymer (eg, a polyvinyl alcohol), which are derived by a dissolution process with the wash water into the water, while the detergent board to a significant proportion of fatty alcohols or similar. which are used to facilitate the formation of the paperboard during production via a melt process.
  • water or solubilizers eg propylene glycol, glycerol
  • polymer eg, a polyvinyl alcohol
  • the task of conserving resources should be to develop a detergent that has the highest possible level of washing-active components and that contains no or only a small proportion of additives such as those mentioned in Tab Fillers, non-woven or molding materials are not required for the core requirement of washing.
  • the CC balance which depends on the technical parameters of the particular detergent, has to consider the physical quantities of volume and mass
  • the volume should be
  • Fertigdosierwaschsch an advantage, since the pollution of water and the environment can be largely avoided by incorrect dosage.
  • Detergent powder and detergent board which opens up the possibility of incorporation of solid components, and the polymer bags filled with liquid detergent are produced in a hot process.
  • the production of detergent powders according to the prior art can be done in two ways. Either a high-pressure spray method is used in which previously mixed slurry of temperature-resistant components of a detergent is dried by means of a spray tower in a hot countercurrent at 1 10 - 130 ° C, followed by the addition of temperature-sensitive components. This procedure is shown in Chart 1.
  • the second way of producing detergent powders is by using an extruder in which premixing of a paste takes place at 80-1 ° C., whereupon
  • cut cylinders are also formed into balls in a round mill at 80-1 ° C., whereupon, as in the first method, temperature-sensitive components are added again.
  • This second method is shown in Chart 2. Production of a round compound extruder mixture
  • temperature resistant are formed into spheres of temperature sensitive components, then components (e.g., detergent by cooling to 30 ° C enzymes, bleach, extruder fragrances
  • the object of the present invention was the development of a highly active ready-to-use detergent (sustainability feature of the consumer application), which is manufactured in the cold process (sustainability feature of the energy balance in production), via the highest possible proportion of washing-active substances (Sustainability feature of the consumer application), via the highest possible proportion of washing-active substances (Sustainability feature of the consumer application).
  • a hydrophobic carrier material 4 which consists of a polymer (consisting of a monomer) in the form of an endless fiber
  • Tab. 3 shows an example produced in a first process step
  • Detergent cloth can be used.
  • a 1-10% by weight solids content 2 is incorporated with stirring and / or dispersion, so that a dispersion 3 is formed.
  • the solid contained zeolites, phyllosilicates and their derivatives
  • the three-phase full-fluid-detergent blanket is shown in FIG. 3 and will be explained in more detail below.
  • Single phase product e.g., zeolite, Schichtsili polypropylene
  • liquid lotion dispersion two-phase product
  • three-phase product three-phase product
  • Solid content Solid content on solid substrate
  • a liquid detergent lotion 1 is prepared with exothermic saponified ingredients and a water content of about 25 wt .-%, wherein the water content may also be lower or higher and generally 10 to 30 wt .-% may be.
  • this lotion 1 using a dispersant solid additives 2 such as zeolites, phyllosilicates, etc. are added, so that the dispersion 3 is formed, wherein the solids content of the dispersion 3 at 5 wt .-%, wherein the solids content may be lower or higher and generally 1 to 10% by weight.
  • the above problem of agglomeration of the zeolites, which opposes a narrow opening gap width 6, was solved by first physically influencing the kinetics of the agglomeration. Firstly, a dispersant was used which distributes the particles 2 in fine form within the lotion 1. The resulting fine distribution in the dispersion 3 was additionally supported by the use of particles as small as possible. The ratio of the size of the particles 2 to the diameter 6 of a round opening or to the gap width 6 of an oblong opening of the particles was found to be decisive for the production of the three-phase solid-state detergent according to the invention
  • the dispersion 3 After the addition of the solids 2, the dispersion 3 has a solids content of 1-10% by weight, that is, e.g. a solids content of 5 wt .-%, on.
  • this dispersion is applied in a moistening system 5 to a carrier material, which is then folded and cut.
  • a hydrophobic material in the form of an endless fiber proved to be effective.
  • Particularly noteworthy here are polypropylene and polyethylene. These materials can be processed in the form of a continuous fiber, whereby the
  • the task of not allowing polymers to reach the groundwater is fulfilled (no dissolution, no microparticles).
  • the carrier material also fulfills the criteria of the delivery of the carrier material into the plastic / packaging waste (eg Grüner Albany) due to the removal of the same after washing by the user.
  • this non-detergent portion unlike e.g. to the polymer bag in the case of ready-to-use liquid detergents - are completely recycled to the recycling cycle.
  • the product definition of the three-phase heavy-duty detergent corresponds to the composition according to Tab. 4, which is particularly suitable for production.
  • Tab.4 Composition of a highly active three-phase heavy-duty cloth (% by weight)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une lingette de détergent universel à trois phases, un système constitué par la lingette de détergent universel à trois phases et un dispositif d'humidification utilisé pour sa fabrication ainsi qu'un procédé pour la fabrication de la lingette de détergent universel à trois phases, une dispersion (3) étant appliquée sur un matériau support (4) solide à température ambiante, caractérisé par les étapes suivantes, consistant à : a) mettre à disposition une lotion de détergent liquide (1) présentant des constituants saponifiés de façon exothermique et une proportion d'eau de 10-30 % en poids; b) ajouter des additifs solides (2) à la lotion de détergent liquide (1) au moyen d'un moyen de dispersion de telle sorte que la dispersion (3) présentant une proportion de solides de 1-10 % en poids se forme; c) appliquer la dispersion (3) sur le matériau support (4) au moyen d'un dispositif d'humidification (5) de manière telle que le matériau support (4) fixe la dispersion (3) de manière statistique; les étapes (a)-(c) ayant lieu à température ambiante et le rapport de la grosseur moyenne de particule des additifs solides (2) au diamètre ou à la largeur de fentes (6) des ouvertures du dispositif d'humidification (5) étant compris entre 5*10-4:1 et 15*10-4:1.
PCT/EP2016/076224 2015-10-30 2016-10-31 Lingette hautement active de détergent universel à trois phases et procédé pour sa fabrication WO2017072358A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES16788534T ES2952137T3 (es) 2015-10-30 2016-10-31 Toallita detergente trifásica altamente activa de lavado completo y procedimiento para su producción
EP16788534.2A EP3368648B1 (fr) 2015-10-30 2016-10-31 Lingette hautement active de détergent universel à trois phases et procédé pour sa fabrication
PL16788534.2T PL3368648T3 (pl) 2015-10-30 2016-10-31 Wysoce aktywna trzyfazowa ściereczka z uniwersalnym środkiem piorącym i sposób jej wytwarzania
RU2018112140A RU2018112140A (ru) 2015-10-30 2016-10-31 Высокоактивная трехфазная салфетка с усиленным моющим средством для стирки и способ получения указанной салфетки
US15/771,042 US20180320114A1 (en) 2015-10-30 2016-10-31 Highly-active three-phase heavy-duty detergent cloth and method for the production thereof
JP2018541522A JP2018534413A (ja) 2015-10-30 2016-10-31 高活性三相重質洗濯洗剤ワイプ及びその製造方法。
CN201680063870.0A CN108473923A (zh) 2015-10-30 2016-10-31 高活性三相重垢洗衣洗涤剂擦及其制造方法
IL258887A IL258887B (en) 2015-10-30 2018-04-24 A very active three-phase cleaning cloth for harsh conditions of use and a method for its production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015014015.9 2015-10-30
DE102015014015.9A DE102015014015A1 (de) 2015-10-30 2015-10-30 Hochaktives Dreiphasen-Vollwaschmitteltuch und Verfahren zu dessen Herstellung

Publications (1)

Publication Number Publication Date
WO2017072358A1 true WO2017072358A1 (fr) 2017-05-04

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ID=57211531

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/076224 WO2017072358A1 (fr) 2015-10-30 2016-10-31 Lingette hautement active de détergent universel à trois phases et procédé pour sa fabrication

Country Status (10)

Country Link
US (1) US20180320114A1 (fr)
EP (1) EP3368648B1 (fr)
JP (1) JP2018534413A (fr)
CN (1) CN108473923A (fr)
DE (1) DE102015014015A1 (fr)
ES (1) ES2952137T3 (fr)
IL (1) IL258887B (fr)
PL (1) PL3368648T3 (fr)
RU (1) RU2018112140A (fr)
WO (1) WO2017072358A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020148301A1 (fr) * 2019-01-15 2020-07-23 Coin Consulting GmbH Lingette de détergent à forte pouvoir de diffusion, à propriétés de durabilité doubles

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017200139A1 (de) * 2017-01-08 2018-07-12 Coin Consulting GmbH Waschmitteltuch mit kontrollierter Aktivierung der waschaktiven Substanzen
DE102021212785A1 (de) 2021-11-13 2023-05-17 Coin Consulting GmbH Feuchttuch mit biologisch abbaubarem verbundträger

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6130193A (en) * 1998-02-06 2000-10-10 Precision Fabrics Group, Inc. Laundry detergent compositions containing silica for laundry detergent sheets
DE102010060126A1 (de) 2010-10-22 2012-04-26 Albaad Deutschland Gmbh Feuchtes Waschmitteltuch
DE102013014015A1 (de) 2013-08-26 2015-02-26 Coin Consulting Ug (Haftungsbeschränkt) Dreiphasen-Vollwaschmitteltuch
WO2015027970A1 (fr) * 2013-08-26 2015-03-05 Coin Consulting Ug (Haftungsbeschränkt) Lingette triple phase contenant un détergent et son procédé de fabrication

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Publication number Priority date Publication date Assignee Title
US6864196B2 (en) * 1995-12-19 2005-03-08 Newlund Laboratories, Inc. Method of making a laundry detergent article containing detergent formulations
ES2193405T3 (es) * 1996-12-09 2003-11-01 Kao Corp Articulo impregnado de detergente.
US8066956B2 (en) * 2006-12-15 2011-11-29 Kimberly-Clark Worldwide, Inc. Delivery of an odor control agent through the use of a presaturated wipe
DE102014008585A1 (de) * 2014-06-17 2015-12-17 Coin Consulting Ug (Haftungsbeschränkt) Vollwaschmitteltuch mit regulierter Phasenaustrittsdiffusion der waschaktiven Substanzen
DE102014012380A1 (de) * 2014-08-25 2016-02-25 Coin Consulting Ug (Haftungsbeschränkt) Vollwaschmitteltuch mit waschaktivem Substrat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6130193A (en) * 1998-02-06 2000-10-10 Precision Fabrics Group, Inc. Laundry detergent compositions containing silica for laundry detergent sheets
DE102010060126A1 (de) 2010-10-22 2012-04-26 Albaad Deutschland Gmbh Feuchtes Waschmitteltuch
DE102013014015A1 (de) 2013-08-26 2015-02-26 Coin Consulting Ug (Haftungsbeschränkt) Dreiphasen-Vollwaschmitteltuch
WO2015027970A1 (fr) * 2013-08-26 2015-03-05 Coin Consulting Ug (Haftungsbeschränkt) Lingette triple phase contenant un détergent et son procédé de fabrication

Non-Patent Citations (1)

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Title
PQ CORPORATION: "Doucil MAP Zeolites For Detergents Applications", 1 June 2009 (2009-06-01), XP055337019, Retrieved from the Internet <URL:http://www.amphochem.com/local/site/files/PQ Doucil MAP brochure.pdf> [retrieved on 20170119] *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020148301A1 (fr) * 2019-01-15 2020-07-23 Coin Consulting GmbH Lingette de détergent à forte pouvoir de diffusion, à propriétés de durabilité doubles

Also Published As

Publication number Publication date
RU2018112140A3 (fr) 2019-12-02
IL258887A (en) 2018-06-28
CN108473923A (zh) 2018-08-31
RU2018112140A (ru) 2019-12-02
EP3368648C0 (fr) 2023-06-07
EP3368648B1 (fr) 2023-06-07
JP2018534413A (ja) 2018-11-22
EP3368648A1 (fr) 2018-09-05
DE102015014015A1 (de) 2017-05-04
ES2952137T3 (es) 2023-10-27
PL3368648T3 (pl) 2024-02-05
IL258887B (en) 2021-12-01
US20180320114A1 (en) 2018-11-08

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